title: Catalytic ketyl-olefin cyclizations enabled by proton-coupled electron transfer.
abstract: Concerted proton-coupled electron transfer is a key mechanism of substrate activation in biological redox catalysis. However, its applications in organic synthesis remain largely unexplored. Herein, we report the development of a new catalytic protocol for ketyl-olefin coupling and present evidence to support concerted proton-coupled electron transfer being the operative mechanism of ketyl formation. Notably, reaction outcomes were correctly predicted by a simple thermodynamic formalism relating the oxidation potentials and pKa values of specific Brønsted acid/reductant combinations to their capacity to act jointly as a formal hydrogen atom donor.
authors.affiliation: Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.
authors.forename: Kyle T
authors.initials: KT
authors.lastname: Tarantino
authors.forename: Peng
authors.initials: P
authors.lastname: Liu
authors.forename: Robert R
authors.initials: RR
authors.lastname: Knowles
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D004583:Electrons; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D011522:Protons; D013816:Thermodynamics
chemical_list: D000475:Alkenes; D007659:Ketones; D011522:Protons